Manufacture of photographic color images



Patented Feb. 2, 1954 2,668,112 ICE MANUFACTURE OF PHOTOGRAPHIC GOLOR IIVIAGES Arthur Henri de Cat, Kessel-Loo, Louvain, Gerard Michiel Sevens, Berchem-Antwerp, and Andi- Emile Van Dormael, Heverlee-Louvain, Belgium, assignors to G'evaert Photo-Producten N. V., Mortsel, Belgium, a company of Belgium No Drawing. Application December 15, 1951,

Serial No. 261,932

Claims priority, application Belgium j December 20, 1950 13 Claims. 1

.This invention relates .to a. process for the manufacture of photographic color images by color development in the presence of a color coupler, to photographic developers which contain such color couplers, to photographic material which, contains such color couplers, and to photographic images obtained according to the process referred to.

It is known to obtain a photographic color image by developing a reducible silver salt image in the presence of a color coupler, i. e., a compound which during development couples with the oxidation product of the developing agent and forms a dyestuff that precipitates onto the developed silver grains.

Yellow and magenta color images are'usually obtained by development in the presence of compounds which contain an active methylene group, for instance, compounds wherein the methylene group is connected at one side to a heterocyclic ring and at the other side to another group capable of activating a methylene group, such as, a cyanor a carbonyl group.

In this class we now have found new color couplers which on color development yield dyestuffs having a favorable absorption for color photography.

It is an object of the present invention toprovide a new process for the production of a photographic color image.

It is another object of the present invention to provide a photographic developing solution containing a new class of color couplers.

It is a further object of the-present invention to providea-photographic material containing a new class of color couplers.

Further objects of-the present inventionwill appear from the following description.

According to'the present invention, a reducible silver salt image is developed with a primary amino aromatic developing agent in the presence of a compound according to the following formula:

(I) C O I 7" F c-ormco-a N V or one. of its tautomeric forms, wherein Z is arylene, .-CO-R is an acyl-, an ester-, an amide-, ahydrazidew or a hydroxamic acid group.

A tautomeric form of Formula I is, for instance, that wherein the CONH- group is replaced by --C(OH) =N-.

.fl hesecompounds may be-..obtained; .e therrbv causing anthranilic. acid or a derivative-thereof to react with the imino ether of cyan "acetic" ester, analogously with the method described by A. Finger and L. Schupp in J. Pr. Chem. (2) '74 (1906) 154, or by effecting a ring closure in an anthranilic acid or -amide, wherein the amino developer or to a colloid layer, a light-sensitive group is substituted by R.CO.CH2.CO, R.CO' having the same significance as indicated hereinbefore, in analogy with the method described by Tomisk and Christensen in J. Am. Chem. Soc.

The presence of the color couplers according to our invention during color development may arise from the adding to the photographic material, or to the developer, a compound which differs from the color coupler only insomuch as in the active CH2- group one or two hydrogen atoms are replaced by a group splitting 01f either before or during the color development.

Our new color couplers may be added to the The aromatic amino compounds, which according to our invention are added to the developer, comprise the mono-, diand triamino aryl compound. As mono-amino developers may be mentioned amino-phenols and amino-cresols and their halogen derivatives, and also amino naphthols.

The developers preferred for our purposesare the aromatic orthoand paradiamines, suchas, paraphenylene diamines and their substitution products.

The following examples serve to illustratethe invention without limiting, however, the scope,

thereof.

Example 1 7.95 g. imino ether of cyan acetic acid ethyl ester and 6.85 g. anthranilic acid are refluxed for 5 hours in 30 com. alcohol. After cooling, the precipitate formed is sucked off and recrystallized from ethanol. The 2-carbethoxymethyl-4-quinazolone thus obtained corresponds to the following formula:

Melting point: 163 C.

A photographic film strip is developed in a bath of the following composition:

(A) NzN-diethyl-p-phenylene diamine hydrochloride g 2 Sodium sulphite (cryst.) g 25 Sodium carbonate (cryst.) g 60 Sodium hydroxide g 2 Water to 1000 ccm.

(B) Quinazolone derivative according to Formula II g 3 CHsOH or acetone ccm 1000 For use, (B) is added to (A) while stirring. The developed image is rinsed for 30 minutes and the silver is removed in the following bath:

Potassium ferricyanide g 50 Potassium bromide g 3 Water to 1000 com.

The image is again rinsed for 10 minutes and then fixed for 20 minutes in the following bath:

Sodium thiosulphate g 250 Water to 1000 com.

and again rinsed for 30 minutes. An intense yellow image with an absorption maximum at about 450 ml is obtained.

Example 2 To 4.4 g. of the compound according to Formula II, dissolved in 100 com. alcohol, 0.6 g. hydrazine dissolved in a minimum of alcohol are added. The mixture is boiled for 1 hour on the water bath and the precipitate formed is recrystallized and washed with ethanol. The product obtained corresponds to the following formula:

(III) (i-CIEh-OO-NH-NH:

Melting point: 260 C.

When treating an exposed photographic film strip as is done in Example 1, whereby in the composition (B) the quinazolone derivative according to Formula II is replaced by the derivative according to Formula III, a yellow image is obtained.

Emmple 3 2.78 g. hydroxylamine hydrochloride and 0.92 g. sodium are dissolved in 50 com. pure alcohol, and 4.6 g. of the compound according to Formula II are added. This mixture is heated for 1 hour on the water bath. After cooling, a precipitate is formed which is washed with. ethanol. The hydroxamic acid obtained corresponds to the following formula:

r m V 0 C-CH2C/ N NH-0H Melting point: 205-210" C.

When treating an exposed photographic film strip as is done in Example 1, whereby in the composition (B) the quinazolonei derivative according to Formula II is replaced by the derivative according to Formula IV, an intense yellow image is obtained.

Example 4 10 g. 4-nitro-anthranilic acid and 12 g. imino ether of cyan acetic acid ethyl ester are melted together at 60 C. for 4 hours on the water bath. The product obtained is recrystallized from methanol and corresponds to the following formula:

Melting point: -168 C.

When treating an exposed photographic film strip as is done in Example 1, whereby in the composition (B) the quina-zolone derivative according to Formula II is replaced by the derivative according to Formula V, an orange image with an absorption maximum at 465 m is obtained.

Example 5 The compound according to Formula V is dissolved in ethanol and catalytically reduced under 1 to 2 atmosphere pressure with Raney nickel. After evaporation of the alcohol, the amino derivative according ot the following formula:-

17TH Emu C-CHPOOO GiHi is obtained.

Melting point: ISO- C.

When treating an exposed photographic film strip as is done in Example 1, whereby in the composition (B) the quinazolone derivative according to Formula II is replaced by the derivative according to Formula VI, an intense yellow image with an absorption maximum at 450 m is obtained.

Example 6 To 3.4 g. anthranil amide dissolved in 10 com. chloroform are added 2.1 g. diketene. The mixture isheated until a homogeneous solution is obtained. This solution is left for 24 hours at room temperature whereafter the precipitate formed is sucked off. After recrystallization from ethanol, aceto-acethyl anthranil amide is obtained. Melting point: 142-144 C. 5.5 g. of the product obtained are dissolved in 10 com. aqueous solution of NaOI-I 5%. The solution is heated on the water bath for 40 minutes and neutralized with acetic acid to pH 7. The precipitate formed is sucked ed and recrystallized from dioxane. The compound obtained corresponds to the following formula:

(VII) G O Melting point: 212-213 C.

When treating an exposed photographic film strip as is done in Example 1, whereby in the composition (B) the quinazolone derivative according to Formula II is replaced by the derivative according to Formula VII, an intense yellow image is obtained.

Example 7 2.05 g. imino ether of para-methyl cyanacetophen m and 1.33- .s.. ant ranilic. arid-are heated together 1 on thenbo-iling waiter bath,f After 2.0- minutes,;the mass melts. but. heating is; continued, for 5 more hours. The precipitate formed is recrystallized from glycol-monomethyl ether. The product obtained corresponds to the following formula:

(VIII CO (Loni-o o-Oom \N% Melting point: above 250 C.

When treating an exposed photographic film strip as is done in Example 1, whereby in the composition (B) the quinazolone derivative according to Formula II is replaced by the derivative according to Formula VIII, an intense yellow image is obtained.

Example 8 3.6 g. imino ether of furoyl acetonitrile and 2.74 g. anthranilic acid are melted together on the boiling water bath and then heated for 3 hours. The oil obtained is shaken with an aqueous solution, of NazCOs and the solution obtained is acidified with acetic acid. The precipitate formed is sucked off. The compound obtained corresponds to the following formula:

(IX) C O Melting point: ab.ove 250 C.

When treating an exposed photographic film strip as is done in Example 1, whereby in the composition (B) thequinazolone derivative according to Formula II is replaced by the derivative according to Formula IX, an intense yellow-orange image is obtained.

Example 9 1.87 g. 2-amino-1-naphtoic acid and 2.40 g. imino ether of cyan acetic acid ethyl ester are heated together for 2 hours at 60 C. on the water bath. The: solid product. formed is. recrystallized from dioxane. Melting, point: 183-185 C. The compound obtained corresponds to the following formula:

When treating an exposed photographic film strip as is done in Example 1, whereby in the composition (B) the quinazolone derivative according to Formula II is replaced by the derivative according to Formula X, an intense yellow image is obtained.

Example 1 0 2.18 g. quinazolonyl acethydrazide according to Formula III and 3.24 g. hexadecyl succinic acid anhydride are refluxed for 3 hours in com. dioxane. After cooling, the precipitate formed is separated by filtration and purified by dissolving in an aqueous solution of NaOI-I 2N and precipitating with an aqueous solution of I-ICl 2N. After recrystallization from dioxane, the melting po nt is lfiaello: c. 'rhmomnound obtained.

corresponds to the following formula:

1 g. of'this product is dissolved in 15 com. of a N aqueous solution of NaOH. Water is added until the volume of the solution reaches 25 com. This solution is added to com. of an emulsion for'positive cin film. This emulsion is coated, onto afilm support,.exposed and developed in the following bath:

N,N-diethyl p phenylene-diamine hydrochloride g 5 Sodium sulphite (cryst.) g 10 Sodium carbonate (cryst.) g 100 Sodium hydroxide g 1 Water to 1000 ccm.

washed, bleached in order to remove the silver, and fixed as in Example 1. A yellow-orange image is obtained.

We claim:

1. Process for the production. of aphotographic color image by developing a reducible silver salt image with a primary amino aromatic developing agent in the presence of a color coupler corresponding to the following formula:

wherein Z is arylene, --COR is a member selected from the group consisting of an acyl-, an

ester-. and amide-, a hydrazideand a hydroxamic acid group.

3. Process for the production of a photographic color image by developing with a primary amino aromatic developing agent a reducible silver salt image in a photographic material containing a color coupler corresponding to the following formula:

wherein Z is arylene, --COR is a member selected from the group consisting of an acyl-, an

ester-, an amide-, a hydrazideand a hydroxamic I acid group.

4. Photographic developer containing 7 a primary amino aromatic developing agent and a color coupler corresponding to the following formula:

CO I wherein Z is arylene, CO-R is a member selected from the group consisting of an acyl-, an ester-, an amide-, a hydrazideand a hydroxamic acid group.

6. Photographic developer containing a primary amino aromatic developing agent and a color coupler corresponding to the following formula:

N wherein Z is arylene, -C-R, is acyl.

'7. Photographic developer containing a primary amino aromatic developing agent and a color coupler corresponding to the following formula:

IIIH C-CHz-O O-R wherein Z is arylene, COR is a hydrazide group.

8. Light-sensitive photographic material comprising a silver halide emulsion layer and a compound corresponding to the following formula:

wherein Z is arylene, -CO--R is a hydrazide group.

8 V p 9. Photographic developer containing mary amino aromatic developing agent compound having the following formula:

a pri- 10. Photographic developer containing mary amino aromatic developing agent compound having the following formula:

a priand a N 11. Photographic developer containing mary amino aromatic developing agent compound having the following formula:

12. Photographic developer containing mary amino aromatic developing agent compound having the following formula:

a priand a a pri- 13. Light-sensitive photographic material comprising a silver halide emulsion layer and a compound having the following formula:

ARTHUR HENRI DE CAT. GERAED MICHIEL SEVENS. ANDRE EMILE VAN DORMAEL.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,396,917 Hanford et al Mar. 19, 1946 2,408,633 Guenther et al Oct. 1, 1946 and a and a' 

1. PROCESS FOR THE PRODUCTION OF A PHOTOGRAPHIC COLAR IMAGE BY DEVELOPING A REDUCIBLE SIVLER SALT IMAGE WITH A PRIMARY AMINO AROMATIC DEVELOPING AGENT IN THE PRESENCE OF A COLOR COUPLER CORRESPONDING TO THE FOLLOWING FORMULA: 